High acrylonitrile high solids containing latices



United States Patent C) 3,227,673 HIGH AQRYLONITRILE HIGH SOLIDS CGNTAINING LATICES June T. Duke and Dorothy C. Prenl, Maple Heights, and Edwin 0. Hook, Chagrin Falls, Qhio, assignors to The Standard Oil Company, Qieveland, Ohio, a corporation of Ghio No Drawing. Filed June 5, 1962, Ser. No. 200,067 1 Claim. (Cl. 260-29.?)

This invention relates to a terpolymer combined with a novel emulsifier-stabilizer, promoter, initiator system to form a latex having excellent film-forming properties. The terpolymer contains a high amount of acrylonitrile and the latex contains a high amount of solids. Films prepared from it have excellent chemical and physical properties.

It has heretofore been impossible to make a high acrylonitrile content latex with good film-forming prop erties, or one that contains a high amount of solids.

The components of the terpolymer of this invention are 40 to 70% acrylonitrile, 15 to 35% of a conjugated diene and 15 to 35% of a monovinyl ether.

The acrylonitrile has the formula CH =CHCN The conjugated diene has the formula Where R is hydrogen, methyl, and ethyl radicals. The conjugated diene may be butadienedfi; Z-rnethyl butadiene-l,3 (isoprene); 2,3-dimethylbutadiene-1,3; 2-diethyl butadiene-l,3; or 2,3-diethyl butadiene-l,3. The preferred materials are either butadiene-1,3, or Z-methylbutadiene-l,3 (isoprene). The monovinyl ether has the the formula CH2=CHOR where R is methyl, ethyl, propyl, isopropyl, butyl. The ethyl and butyl vinyl ethers are most readily available commercially and the latter is preferred.

When the terpolymer is made up according to the invention, the latex forms clear films with outstanding ph sical properties. Many poiymerization formulas were studied with the terpolymer, but no other system successfully formed clear films with excellent properties. The high acrylonitrile solids latices are suitable for 'coatings and as vehicles for paints, sizes, etc.

The emulsifier consists of phosphate esters of po'lyox ethylenated alk l phenols, such as nonyl phenol, or of polyoxyethylenated aliphatic alcohols, such as tridecyl alcoholwhich are nonionic surfactants in their own right. The emulsifier is either the mono or the diester or a mixture of the mono and diesters with the following formulae:

n is the number of ethylene oxide units required for a water number of at least 18.

The emulsifier is made according to the methods disclosed in the US. Patents 3,004,056 and 3,004,057. In use the pH of the emulsifier-water solution is adjusted by the addition of ammonium, sodium, or potassium hydroxide. The preferred emulsifier is available under the trade name Gafac RE6l0, and the amount is 1.5 to 5 parts per hundred parts of monomer.

For this invention, it was found that it i the water value number of the emulsifier that is the critical factor. The water value number is determined according to the method described in Anal. Chem. 28, p. 1693 (1956). The water value number cannot be less than 18, although the preferred number is 24. There is no critical upper limit for the water value, but it becomes impractical to go above 1000.

The stabilizer is the sodium salt of the formaldehyde condensation product of naphthalene sulfonic acid. This compound is available under the trademarks Daxad and Daxad-l l. Darvan, a purified Daxad, is also suitable. The amount of stabilizer used is 0.1 to 0.5 part per hundred part of monomer.

The promoter is a higher mercaptan and may contain from 8 to 20 carbons. n-Dodecyl mercaptan is preferred. It is used in the amount of 0.005 to 0.5 part per hundred parts of monomer.

The initiator is an oxygenliberating material, such as benzoyl peroxide, sodium persulfate, potassium persulfate, sodium perborate, or hydrogen peroxide. The preferred initiator is potassium persulfate. The amount varies between 0.10 to 1.5 parts per hundred parts of monomer.

The polymerization can be conducted at pH levels of 3 to 9, but adjustment of the emulsifier-Water-stabilizer mixture of pH 7-8 is preferred for polymerization stability.

The amount of water to monomer is based on parts by weight and is 40 to '60 parts of .Water to 60 to 40-of monomer. The water preferably is either distilled or deionized.

It is the emulsifier-stabilizer combination that makes possible the formation of a fluid, stable, high solids containing latex that contains a large amount of acrylonitrile. The polymerization is effected in a short time depending on the initiator-promoter system. The conversions are high. A conversion of of monomer in five hours has been achieved. Untreated monomer can be removed, if desired, by vacuum stripping. Furthermore, the use of this emulsifier-stabilizer system has made possible a latex of at least 45% total solids that is completely free of coaguluin. The films made from the latex are unusually clear and glossy, in addition to being tough and flexible.

Particle size may be varied by altering the initial amount of emulsifier; this, in turn, affects latex viscosity and film properties. Additional amounts of emulsifier are added w-hile polymerization progresses to raise the total to the desired level. Polymerization rate is controlled, as well as latex viscosity, by adding additional amounts of promoter with the emulsifier. Incremental additions of emulsifier and promoter are specified in this high acrylonitrile high solids composition to achieve desirable viscosity, stability, and polymerization rate.

The following examples are set forth as preferred embodiments of the invention. They are not intended, in

any way, to limit the invention.

Example I The emulsifier is prepared by reacting nonyl phenol with ethylene oxide and phosphating the product with P 0 to obtain a product that has a Water balance number of 24. The reaction is exothermic and, in some in stances, cooling is necessary to prevent the temperature from rising above C. since this causes discoloration. The reaction may continue for from one-half to five hours or more at ambient temperatures up to 110 C. until all the P has dissolved. Vigorous agitation helps the reaction go to completion.

The ingredients of the composition are:

4 zation was carried out in a closed stainless steel pressure vessel at 50 to 70 C. At the end of 5.5 hours, the polymer conversion was 85%, the total solids were 43.4%. The latex prepared was free of coagulurn, stable and Puts/100 Pans Parts/100 Parts 5 fluid, and at room temperature, formed at clear, tough,

Monomer, Monomer, flexible glOSSy film. Initial Charge Total Charge Example IV Acrylonitrile 45 45 r i X m 1 1 Tha Butylvmylether 30 30 The emulsifier was prepa ed as E a p e rsoprene 25 25 composition consists of. Emulsifier (Gaiac RE-6l0). a 1. 5 2. 35 Stabilizer (Daxad-ll) 0. 1 0. 1 Initiator (potassium persulfate) B 0.2 0, 5 Parts/100 Parts Parts/100 Parts Promoter (n-dodecyl mercaptan) 0. 04 0. 04 Monomer, Monomer, Water 87.0 100. 0 Initial Charge Total Charge 1\ The rest of the emulsifier, potassium persulfate, and water were Acrylonitrile 45 45 added in three substantially equal increments as follows, at 41, 50 and Ethyl vinyl ether. 30 30 05 percent conversion. Butadiene d 125 1 Emulsiier a l .5

The pH of the emulsifier and water mixture was ad- Stabiliz er(Daxad11) 0.10 0. 5 a, Initiator (potassium persul 0. 10 yusted to 8.0 with ammonium hydrox de. The pol rrieri Promotgr (mdodecylnmmpmn) M4 (104 zation was carried out in a closed stainless steel pressure Water 37.0 100.0 vessel at 50 to 70 C. At the end of 7.5 hours, the polymer conversion was 88.5, the total solids were 41% h The rest of the emulsifier, initiator, and water was added in three and the nitrogen analysis indicated 50.5% acrylonitrile elements at "W180 percentcowersmn' in the polymer in the latex. The latex prepared was The pH of the emulsifier and water mixture was adiluid, stable, free of coagulum, and at room temperature justed to 8.0-$0.1 with 10% potassium hydroxide soluand below formed clear, glossy, tough, flexible films. tion. Polymerization occurred in a close stainless steel Films may be formed as low as 9 C. These films are pressure vessel at 50 to 70 C. Conversion was 92% resistant to grease and water, and as free films have a at the end of hours, mtal Solids were The tensile strength of at least 1000 p.s.i. amount of acrylonitrile in the polymer in the latex was vam le H 3 58.2% based on a nitrogen analysis. The latex prepared p was free of coagulum and stable. The films that formed The emulsifier was prepared as an Example I. The at room temperature were clear, glossy, tough, and flexicomposition consists of? ble.

Example V P 00 Parts a s/ 00 ts The emulsifier was prepared as in Example I. The

Monomer, Monomer, t Initial Charge Total Charge cOmPQSl 0011515 5 Aerylonitrile 55 55 Parts/100 Partslarts/IOO Parts Butyl vinyl er. 25 2,5 Monomer, Monomer, Butadiene-1,3 20 20 Initial Charge Total Charge Emulsifier (Gafa a 1. 5 2. 35 Stabilizer (Daxad11) 0.1 0.1 Initiator (potassium persuli'ate a 0, 2 0. 4 Acrylolutrile 45. 0 45. 0 Promoter (ii-d0decylniereaptan) 0.04 0.04 Butylvmyl ether- 30.0 30.0 Water a 91.0 100. 0 Isoprene 25, 0 25.0 Emulsitier (Gaiae RE-Sl a 1. 50 2. 35 Stabilizer (Daxafhll) 0. 10 0. 10 B The rest of the emulsifier, initiator, and water were added in two Initiator (DOtfiSSlulTl p l increments at 65 and 84 percent conversion. Ylyotmoter (n-dodecyl mercaptan) gap: 18603 a er a Ammonium hydroxide was used to adpist the pH of the emulslfiPr and Water mixture to a PH of a The rest of the emulsifier, initiator, and water were added in three polymerization was conducted at 50 to 70 C. in a increments at conversions 0:40, 50, and 05 percent. closed stainless steel reactor. The conversion was 92% 50 The PH f the l ifi and water mixture was dat the end of 7.5 honrs. The total solids was 47.0%. justed to 80:01 with 10% sodium hydroxide solution. The amount 0L acrylomtflle 1n thh P l 1n the latex Polymerization was carried out in a closed stainless steel was 582% based on a nitrogen ahalysls- The latex Was pressure vessel at 50 to 70 C. At the end of 7.5 hours, free 0f Coaghhlm and Stable- The films that formefi at the polymer conversion, the total solids, and the amount room temperature Weft? Clear, glossy, tough and flexlbleof acrylonitrile in the polymer in the latex based on a.

nitrogen analysis, were approximately the same in Exxample III ample I. The latex that was prepared was fluid, stable, The emulsifier was prepared as in Example I. The free of coagulum, and at room temperature and below composition consists of: formed clear, glossy, tough, flexible films.

We claim:

' l tin ial Parts/m0 Parts Parts/m0 Parts A stable high solids atex consis essent ly of Monomer, Monomer, (a) 40 to 60 parts by weight of water; lmtlalohafge Totalcharge (b) 40 to 60 parts by weight of polymerized monomers consisting essentially of Acrylonltrile 45 45 Ethyl vinyl ether- 30 3o (1) 40 to acrylominle Butadiene 25 25 (2) 15 to 35% of a con ugated diene having the Emulsifier (Gafac RIB-610) a 1. 5 2. 35 %tatbiltizer((Dtaxadll) 0. 1 o. 1 formula ni in or p0 assium pers 21 e I 0.2 0.5 H: Promoter (n-dodeeyl mercaptan) 0.04 0. 04 C 2 CH Water 87.0 100.0 P0 R R where R is selected from the group consisting a The rest of the emulsifier, potassium persullate, andwater were added L in three substantially equal increments at 41, 50, and 05 percent conof hydrogen: methyl and efhyl radlcals: velSlOn. (3) 15 to 35% of a monovinyl ether of the gen- The pH of the emulsifier and water mixture was adefal formula justed to 8.0 with ammonium hydroxide. The polymeri- CH =CHOR Where R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl radicals, and based on 100 parts of the monomers; (c) as an emulsifier 1.5 to 5 parts of a compound 5 selected from the group consisting of /O RO(CHzGH,O)nP

RO-(CHzCH:O)n O RO(GH2CHzO) n \OM and mixtures thereof, in which R is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl having 8 to 27 carbon atoms, M is selected from the group consisting of hydrogen, ammonium, potassium and sodium, and n is the number of ethylene 20 units required for a water number of at least 18;

(d) as a stabilizer 0.1 to 0.5 part of a sodium salt of the formaldehyde condensation product of naphthalene sulfonic acid;

References Cited by the Examiner UNITED STATES PATENTS Arundale et a1. 260-29] Beadell 260-823 Eilbeck et al. 260-29] Thompson et al. 260-291 MURRAY TILLMAN, Primary Examiner.

LOUISE P. QUAST, Examiner. 

